Halogenated grafting agents and halogenated branched butyl rubber, as well as methods for producing and using the same.

Abstract

The present invention relates to the field of rubber damping materials, and discloses a halogenated grafting agent, a halogenated branched butyl rubber, and their production methods and uses. The halogenated grafting agent contains a structural unit A, an optional structural unit B, a structural unit C, and a structural unit D. The structural unit A has a structure represented by formula (1), the structural unit C has a structure represented by formula (2), the structural unit B is connected to the structural unit A and the structural unit C respectively, the structural unit D is a terminal capping structural unit, and the structural unit B and the structural unit D are each independently derived from a conjugated diene. The method of the present invention solves the problem of isomerization rearrangement of the halogenated structure with low damping properties in butyl rubber, and not only avoids damage to the mechanical properties and air permeability of butyl rubber by the damping brominated grafting agent, but also improves the damping performance and tensile strength of butyl rubber. 【Chemical 1】 JPEG2025516734000010.jpg48170

Description

Cross-reference of related applications

[0001] This application claims the benefits of Chinese Patent Application No. 202211183875.0, filed on 27 September 2022, the contents of which are incorporated herein by reference. [Technical Field]

[0002] This invention relates to the field of rubber damping materials, and more specifically to halogenated grafting agents and halogenated branched butyl rubber, as well as methods for producing and using them. [Background technology]

[0003] Rubber damping materials, due to the unique viscoelastic properties of polymers, have a clear damping effect that reduces vibration and noise, improving the working environment for both humans and machines. They are widely used in many fields, including high-speed rail, aerospace, naval vessels and ships, mechanical engineering, automobiles, and electronics. In particular, in data storage systems for IT equipment such as various servers, computers, workstations, and switches, fan rotation generates cabinet vibration and noise, which significantly affects the lifespan of hard drives, leading to a very high demand for efficient damping and vibration control products. Furthermore, the operating environments of electronic equipment are facing increasingly complex conditions, such as lower and higher temperatures, resulting in very high demands for rubber damping materials.

[0004] Diene rubbers are widely used in various fields of daily production and life, and their main industrial products include butadiene rubber, isoprene rubber, butyl rubber, and halogenated butyl rubber. Brominated butyl rubber (BIIR) is an important type of halogenated butyl rubber, possessing excellent damping performance and being one of the most widely used basic damping rubbers. However, conventional brominated butyl rubber has drawbacks such as insufficient damping value, insufficient damping performance stability, insufficient effective damping temperature range, and inferior mechanical properties, making it unable to meet the damping performance requirements of materials used in large and precision equipment. This is a bottleneck in expanding the applications of brominated butyl rubber materials.

[0005] CN103113682A discloses a high-performance damping rubber and a method for manufacturing the same. This high-performance damping rubber is obtained by blending and polymerizing a first precursor and a second precursor, wherein the first precursor has molecular chains having cationic groups, and the second precursor has molecular chains having anionic groups, the molar ratio of cationic groups to anionic groups in the rubber is 1:1, the breaking strength is 5 to 20 MPa, the breaking elongation is 200% to 300%, the repair efficiency is high at 90%, and the repair temperature is wide, ranging from 20 to 100°C, resulting in a high-performance damping rubber with high repair efficiency.

[0006] CN103113682A discloses a highly damping material with a wide temperature range for electronic products and a method for manufacturing the same. By forming a supramolecular network structure through the interaction between non-polar butyl rubber, brominated p-tert-octylphenol formaldehyde resin, and polar small molecule hindered phenol A060, the temperature range reaches -60 to 100°C.

[0007] Liao Mingyi et al. (Journal of Dalian Maritime University, 2008, 34(2):83-86) disclosed a stepwise method for improving the damping performance of butyl rubber (IIR). Using IIR as the polymer network and poly(styrene-methyl methacrylate) [P(St-MMA)] as the polymer network II, they produced a butyl rubber / poly(styrene-methyl methacrylate) interpenetrating polymer network [IIR / P(St-MMA)] by graft polymerization, thereby producing a butyl rubber material with a wide temperature range and high damping performance.

[0008] Conventional technologies, such as blending, copolymerization, and interpenetrating network polymer methods, can broaden the effective damping temperature range of rubber and improve its damping performance to some extent. However, these methods still have certain limitations and can lead to a decrease in the mechanical properties of the modified material. [Overview of the Initiative] [Problems that the invention aims to solve]

[0009] The object of the present invention is to provide a halogenated grafting agent and halogenated branched butyl rubber that can be used in the production of halogenated branched butyl rubber to obtain halogenated branched butyl rubber with a high maximum damping rate, as well as a method for producing and using these, in order to solve the problems of the prior art in which rubber materials do not have high damping characteristics and mechanical properties. The method of the present invention solves the problem of isomerization rearrangement of the halogenated structure, which causes low damping in butyl rubber, and not only avoids damage to the mechanical properties and permeability of butyl rubber by damping brominated grafting agents, but also improves the damping performance and tensile strength of butyl rubber. [Means for solving the problem]

[0010] To achieve the above objective, a first aspect of the present invention provides a halogenation grafting agent comprising structural unit A, an arbitrary structural unit B, structural unit C, and structural unit D, wherein structural unit A has the structure shown by formula (1), structural unit C has the structure shown by formula (2), structural unit B is connected to structural unit A and structural unit C respectively, and structural unit D is a terminal capping structural unit, wherein structural unit B and structural unit D each independently provide a halogenation grafting agent derived from a conjugated diene. [ka] (Here, R1 and R2 are each independently hydrogen or a linear or branched alkyl group of C1-C5, R3 is a linear or branched alkyl group of C1-C8, R4 and R5 are each independently hydrogen or a linear or branched alkyl group of C1-C4, and X is a halogen.)

[0011] A second aspect of the present invention is: Under polymerization reaction conditions, in the presence of an initiator, the monomer represented by formula (I) and the monomer represented by formula (II) are polymerized to obtain a polymerization product. Alternatively, (1) carry out the first polymerization reaction of the monomer represented by formula (I) in the presence of a molecular weight modifier, a first solvent, and a first initiator, and optionally add a second conjugated diene to carry out the first capping reaction to obtain the first product, (2) Step S1, in the presence of a structural modifier, a second solvent, and a second initiator, the monomer represented by formula (II) is subjected to a second polymerization reaction to obtain a second product, the first product is added thereto, and a third polymerization reaction is carried out to obtain a third product. The present invention provides a method for producing a halogenated grafting agent, comprising step S2, which involves carrying out a second capping reaction between the polymerization product obtained in step S1 or the third product obtained in step (2) and the first conjugated diene to obtain the halogenated grafting agent. [ka] (Here, R1 and R2 are each independently hydrogen or a linear or branched alkyl group of C1-C5, R3 is a linear or branched alkyl group of C1-C8, R4 and R5 are each independently hydrogen or a linear or branched alkyl group of C1-C4, and X is a halogen.)

[0012] A third aspect of the present invention provides a halogenated grafting agent produced by the manufacturing method described above.

[0013] A fourth aspect of the present invention provides the use of the aforementioned halogenated grafting agent as a grafting agent for producing diene rubber.

[0014] A fifth aspect of the present invention provides a halogenated branched butyl rubber comprising structural unit E derived from isobutylene, structural unit F derived from isoprene, and structural unit G derived from a halogenated grafting agent, wherein the halogenated grafting agent is the aforementioned halogenated grafting agent.

[0015] A sixth aspect of the present invention is: Provided is a method for producing a halogenated branched butyl rubber, including the step of cationically polymerizing isobutylene, isoprene, and the aforementioned halogenated grafting agent in the presence of a diluent, an organic solvent, and a co-initiator to obtain the halogenated branched butyl rubber.

[0016] A seventh aspect of the present invention provides a halogenated branched butyl rubber obtained by the aforementioned production method.

[0017] An eighth aspect of the present invention provides the use of the aforementioned halogenated branched butyl rubber in automobiles and electronic and electrical devices.

Advantages of the Invention

[0018] According to the above technical solution, the beneficial technical effects obtained by the present invention are as follows.

[0019] (1) The halogenated grafting agent according to the present invention has a p-alkylphenyl structural unit and a haloalkyl structural unit bonded on a polymer chain. Its molecular chain has the characteristics of high rigidity, large steric hindrance, strong adsorption force, and many active sites. Thereby, the p-alkylphenyl and halogen atoms can produce a remarkable "synergistic effect" when improving the damping property of the material. When using this halogenated grafting agent to produce a halogenated branched butyl rubber as a halogenated grafting agent, the damping performance of the halogenated branched butyl rubber can be greatly improved, and a high-damping halogenated branched butyl rubber with a high maximum damping rate can be produced.

[0020] (2) In the present invention, the halogenated grafting agent produced by free radical polymerization and anionic polymerization contains a non-polar p-alkylbenzene ring structure. The benzene ring has the characteristics of high rigidity and large steric hindrance. It not only avoids the problem that the molecular weight distribution of butyl rubber broadens due to branching and the mechanical properties and airtightness of butyl rubber decrease, but also improves the tensile strength of butyl rubber.

[0021] (3) The halogenated branched butyl rubber produced by the present invention is produced not by ion substitution, but by addition polymerization using a polymeric damping halogenated grafting agent. The p-alkylphenyl and s-position bromine-halogen structures in the grafting agent are embedded in the main segment of the butyl rubber, blocking the isomerization conditions of the molecular structure, improving the stability of the damping performance of the halogenated branched butyl rubber, and expanding the range of applications for high damping halogenated branched butyl rubber.

[0022] (4) In the manufacturing process of high-damping halogenated branched butyl rubber, the present invention eliminates the emission of volatile organic compounds (VOCs) and by-products HBr, reduces harm to the human body and the environment, and omits the process of recovering by-products HBr by alkaline washing. The manufacturing method is environmentally friendly, has a short process time, low production costs, and is suitable for industrial production. [Brief explanation of the drawing]

[0023] [Figure 1] This is the infrared spectral chart of the halogenated grafting agent obtained in Production Example 1. [Modes for carrying out the invention]

[0024] The endpoints and any values ​​of the ranges disclosed herein are not limited to precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to them. In the case of numerical ranges, the intervals between the endpoint values ​​of individual ranges, the intervals between the endpoint values ​​of individual ranges and individual point values, and the intervals between individual point values ​​can be combined to obtain one or more new numerical ranges, and these numerical ranges should be considered as specifically disclosed herein.

[0025] A first aspect of the present invention provides a halogenation grafting agent comprising structural unit A, an arbitrary structural unit B, structural unit C, and structural unit D, wherein structural unit A has the structure shown by formula (1), structural unit C has the structure shown by formula (2), structural unit B is connected to structural unit A and structural unit C respectively, and structural unit D is a terminal capping structural unit, wherein structural unit B and structural unit D are each independently derived from a conjugated diene. [ka] (In this case, R1 and R2 are each independently hydrogen or a C1-C5 linear or branched alkyl group, R3 is a C1-C8 linear or branched alkyl group, R4 and R5 are each independently hydrogen or a C1-C4 linear or branched alkyl group, and X is a halogen.)

[0026] The halogenated grafting agent of the present invention has p-alkylphenyl structural units and haloalkyl structural units bonded to a polymer chain, and the molecular chain is characterized by high rigidity, high steric hindrance, strong adsorption, and a large number of active sites. Furthermore, because conjugated diene structural units are contained at the ends of the copolymer, this multi-component copolymer has high polymerization activity and can be used as a grafting agent for the production of branched diene rubber, particularly halogenated branched diene rubber.

[0027] The grafting agent of the present invention contains numerous regularly arranged benzene ring structures, fully exhibiting its characteristics of high rigidity and high steric hindrance, and can significantly improve the elastic modulus and barrier properties of halogenated grafting agents. The halogenated branched diene rubber produced using this grafting agent has high damping performance while maintaining excellent mechanical strength and airtightness.

[0028] The stability of the bromine structure in the grafting agent of the present invention not only improves the damping performance of halogenated branched diene rubber, but also solves the problem of butyl rubber, which has few double bonds due to its high saturation and is difficult to vulcanize. This helps to increase the vulcanization rate and improve the vulcanization processability of halogenated branched diene rubber.

[0029] Therefore, the grafting agent of the present invention is characterized by numerous benzene ring structures, a stable halogen structure, and high isotacticity. The halogenated branched diene rubber produced using this grafting agent not only has high damping performance but also excellent airtightness, mechanical strength, and vulcanization processability, meeting the requirements of various applications.

[0030] In the present invention, the examples of the C1-C8 linear or branched alkyl groups may be any one of the following: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, n-hexyl, isohexyl, n-heptyl, isoheptyl, 2-methylhexyl, 2-ethylhexyl, 1-methylheptyl, 2-methylheptyl, n-octyl, and isooctyl.

[0031] In some embodiments, R1 and R2 are each independently hydrogen or a C1-C3 linear or branched alkyl group, preferably hydrogen, methyl, ethyl, or propyl.

[0032] In some embodiments, R3 is a C1-C5 linear or branched alkyl group, preferably methyl, ethyl, n-propyl, or isopropyl.

[0033] In some embodiments, R4 and R5 are each independently hydrogen or a C1-C2 alkyl group, preferably hydrogen, methyl, or ethyl.

[0034] In some embodiments, X is at least one selected from Cl and Br, preferably Br.

[0035] In some embodiments, the conjugated diene is butadiene and / or isoprene.

[0036] In some preferred embodiments of the present invention, the structural unit represented by formula (1) may be a structural unit derived from p-alkylstyrene, for example, p-methylstyrene, p-ethylstyrene, p-propylstyrene, pn-butylstyrene, p-isobutylstyrene, or p-isopentylstyrene.

[0037] In some preferred embodiments of the present invention, the structural unit represented by formula (2) may be a structural unit derived from a halogenated olefin, such as vinyl bromide, vinyl chloride, 1-bromo-1-propene, 2-bromo-1-propene, 1-bromo-1-butene, or 2-bromo-1-butene, but is preferably a structural unit derived from vinyl bromide or 2-bromo-1-butene.

[0038] In order to improve the maximum damping rate, air permeability, and tensile strength of halogenated branched butyl rubber, in some embodiments, the mass ratio of structural unit A, structural unit B, structural unit C, and structural unit D is 100:0~2:15~70:3~7, for example, 100:0.3:30:4, 100:0.5:40:5, 100:0.6:50:6, 100:0.8:60:7, 100:0.9:70:5, 100:1:65:4, 100:1.2:50:5, 100:1.3:55:6, 100:1.4:45:3, 100:1.5:80:5, 100:1.8:78:5, and any value within the range of any two of the above values, preferably 100:0.3~1.5:30~68:4~6. When the mass ratio of each structural unit satisfies this range, the resulting halogenated branched butyl rubber has a maximum damping rate of tanδ max The ratio is 1.5 or higher, and the air permeability is 20.215 to 21.251 cm. 3 The tensile strength is 17.6 MPa to 20.6 MPa.

[0039] In this invention, the mass ratio of each structural unit may be expressed as the input mass ratio of the monomer corresponding to each structural unit.

[0040] In some embodiments, structural unit B is derived from butadiene, and structural unit D is derived from isoprene.

[0041] In a preferred embodiment, the structure of the halogenated grafting agent of the present invention is represented by the general formula I1-A1-B1-C-B2-A2-I2, where I1 and I2 are structural units derived from isoprene, A1 and A2 are structural units represented by formula (1), B1 and B2 are structural units derived from butadiene, and C is a structural unit represented by formula (2).

[0042] In some embodiments, the halogen content in the halogenated grafting agent is 3 to 7 wt%, preferably 4 to 6 wt%, by mass percentage.

[0043] In this invention, the halogen content is measured using a Q600 TG / DTG thermogravimetric analyzer.

[0044] In some embodiments, the number-average molecular weight of the halogenated grafting agent is 25,000 to 50,000 g / mol, preferably 30,000 to 40,000 g / mol.

[0045] In some embodiments, the molecular weight distribution index (Mw / Mn) of the halogenated grafting agent is any value within the range of 1.5 to 4, for example, 1.6, 1.9, 2, 2.5, 2.8, 3, 3.5, 3.7, and any two of the above values, preferably 2 to 3.5.

[0046] In some embodiments, the halogenated grafting agent is a block copolymer or a random copolymer.

[0047] In some embodiments, the halogenated grafting agent has an apparent viscosity of 5 to 35 mPa·s at 25°C.

[0048] In this invention, the apparent viscosity of the halogenated grafting agent is tested using an Ubbelohde viscometer according to the GB / T 10247-2008 viscosity measurement method.

[0049] A second aspect of the present invention is: Under polymerization reaction conditions, in the presence of an initiator, the monomer represented by formula (I) and the monomer represented by formula (II) are polymerized to obtain a polymerization product. Alternatively, (1) carry out the first polymerization reaction of the monomer represented by formula (I) in the presence of a molecular weight modifier, a first solvent, and a first initiator, and optionally add a second conjugated diene to carry out the first capping reaction to obtain the first product, (2) Step S1, in the presence of a structural modifier, a second solvent, and a second initiator, the monomer represented by formula (II) is subjected to a second polymerization reaction to obtain a second product, the first product is added thereto, and a third polymerization reaction is carried out to obtain a third product. The present invention provides a method for producing a halogenated grafting agent, comprising step S2, which involves carrying out a second capping reaction between the polymerization product obtained in step S1 or the third product obtained in step (2) and the first conjugated diene to obtain the halogenated grafting agent. [ka] (Here, R1 and R2 are each independently hydrogen or a linear or branched alkyl group of C1-C5, R3 is a linear or branched alkyl group of C1-C8, R4 and R5 are each independently hydrogen or a linear or branched alkyl group of C1-C4, and X is a halogen.)

[0050] In some embodiments, R1 and R2 are each independently hydrogen or a C1-C3 linear or branched alkyl group, preferably hydrogen, methyl, ethyl, or propyl.

[0051] In some embodiments, R3 is a C1-C5 linear or branched alkyl group, preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, or isopentyl.

[0052] In some embodiments, R4 and R5 are each independently hydrogen or a C1-C2 alkyl group, preferably hydrogen, methyl, or ethyl.

[0053] In some embodiments, X is at least one selected from Cl and Br, preferably Br.

[0054] The present invention provides a method for producing highly damped halogenated branched butyl rubber by first synthesizing an anionically reactive polymer halogenating agent, then synthesizing a polymer damped halogenated grafting agent from p-alkylstyrene and this polymer halogenating agent using alkyllithium as an initiator, and finally performing cationic polymerization of this polymer damped halogenated grafting agent, isobutylene, and isoprene in the presence of a composite catalyst system of alkylaluminum halide and protic acid. In the grafting agent of the present invention, the introduction of benzene rings and halogen atoms and the use of anionic polymerization methods result in a highly regular arrangement of benzene rings and halogen atoms, increasing the steric hindrance effect of the molecular chains and strengthening the polarity of the grafting agent. As a result, the migration resistance of the segments increases, internal friction increases, and the relaxation tension of the segments increases. In this way, damage to the mechanical properties and permeability of the butyl rubber by the damped halogenated grafting agent is avoided during the grafting process of butyl rubber, and the damping performance and tensile strength of the butyl rubber are improved.

[0055] According to the method of the present invention, the maximum damping rate is high, and furthermore, tanδ max This makes it possible to manufacture high-damping halogenated branched butyl rubber with a damping ratio of 1.5 or higher.

[0056] In some embodiments, the mass ratio of the monomer represented by formula (I), the second conjugated diene, the monomer represented by formula (II), and the first conjugated diene is 100:0 to 2:15 to 70:3 to 7, for example, 100:0.3:30:4, 100:0.5:40:5, 100:0.6:50:6, 100:0.8:60:7, 100:0.9:70:5, 100:1:65:4, 100:1.2:50:5, 100:1.3:55:6, 100:1.4:45:3, 100:1.5:80:5, 100:1.8:78:5, and any value within the range of any two of the above values, preferably 100:0.3 to 1.5:30 to 68:4 to 6.

[0057] In the present invention, by controlling the mass ratio of the monomer represented by formula (I), the second conjugated diene, the monomer represented by formula (II), and the first conjugated diene within a specific range, a normal reaction for producing polymer grafting agents and grafted butyl rubber can be ensured.

[0058] In this invention, the second conjugated diene and the first conjugated diene are used as end-capping agents. The amount used significantly affects the polymerization reaction. Too much increases the flexibility of the grafting agent segments, impairing the damping performance and mechanical strength of the butyl rubber. Too little results in insufficient end-capping, reducing the reaction-active sites and decreasing the grafting rate, which in turn reduces the damping performance and mechanical strength of the butyl rubber.

[0059] In some embodiments, the monomer represented by formula (II) is a halogenated olefin, preferably at least one selected from vinyl bromide, vinyl chloride, 1-bromo-1-propene, 2-bromo-1-propene, 1-bromo-1-butene, and 2-bromo-1-butene, preferably vinyl bromide or 2-bromo-1-butene.

[0060] In some embodiments, the monomer represented by formula (I) is p-alkylstyrene, preferably at least one selected from p-methylstyrene, p-ethylstyrene, p-propylstyrene, pn-butylstyrene, p-isobutylstyrene, and p-isopentylstyrene, preferably p-methylstyrene.

[0061] In some embodiments, the second conjugated diene is butadiene and / or isoprene, preferably isoprene.

[0062] In some embodiments, the first conjugated diene is preferably 1,3-butadiene, which is butadiene and / or isoprene.

[0063] In some embodiments, the first initiator is an organic peroxide, preferably at least one selected from dicumyl peroxide (DCP), cumene hydroperoxide, and benzoyl peroxide (BPO), more preferably benzoyl peroxide (BPO).

[0064] In some embodiments, the second initiator is a hydrocarbyl monolithium compound R-Li, where R is a saturated aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, or a composite group of the above, containing 1 to 20 carbon atoms, preferably at least one selected from n-butyllithium, sec-butyllithium, methylbutyllithium, phenylbutyllithium, naphthyllithium, cyclohexyllithium, and dodecyllithium, more preferably n-butyllithium.

[0065] In some embodiments, the molecular weight modifier is at least one selected from tert-decyl mercaptan, tert-dodecyl mercaptan, tert-tetradecyl mercaptan, and tert-hexadecyl mercaptan, preferably tert-dodecyl mercaptan.

[0066] In some embodiments, the structural modifier is a polar organic compound, preferably at least one selected from diethylene glycol dimethyl ether (DGE), tetrahydrofuran (THF), ethyl ether, ethyl methyl ether, anisole, diphenyl ether, glycol dimethyl ether (DME), and triethylamine, more preferably tetrahydrofuran (THF).

[0067] The structural modifier of the present invention is a polar organic compound that generates a solvation effect in the polymerization system and is used to adjust ionic reactivity. It can adjust the reactivity ratio of p-alkylstyrene and isoprene, allowing both to be randomly copolymerized.

[0068] In some embodiments, the first solvent and the second solvent are each independently a hydrocarbon solvent, preferably at least one selected from linear alkanes, aromatic hydrocarbons, and cycloalkanes, and more preferably at least one selected from pentane, hexane, octane, heptane, cyclohexane, benzene, toluene, xylene, and ethylbenzene.

[0069] In the present invention, the amounts used for molecular weight modifiers, structural modifiers, solvents, etc., are not particularly limited and may be added in amounts commonly used in the field.

[0070] In some embodiments, the conditions for the first polymerization reaction include a reaction temperature of 50-60°C and a reaction time of 4-6 hours.

[0071] In some embodiments, the conditions for the first capping reaction include a reaction temperature of 50-60°C and a reaction time of 20-40 min.

[0072] In some embodiments, the conditions for the second polymerization reaction include a reaction temperature of 60-70°C and a reaction time of 70-90 min.

[0073] In some embodiments, the conditions for the third polymerization reaction include a reaction temperature of 80-90°C and a reaction time of 80-100 min.

[0074] In some embodiments, the conditions for the second capping reaction include a reaction temperature of 80-90°C and a reaction time of 30-40 min.

[0075] The method of the present invention further comprises the step of adding an inhibitor to stop the reaction after polymerization is complete, wherein the inhibitor may be one or more selected from methanol, ethanol, and ethanol.

[0076] In this invention, the polymerization reaction is carried out without oxygen and water, preferably in an inert gas environment. Both the polymerization process and the dissolution process are carried out in a hydrocarbon solvent.

[0077] In this invention, vinyl bromide and p-methylstyrene are polymerized directly without adding a capping agent during the process. Since vinyl bromide cannot undergo anionic polymerization, only free radical polymerization, in which an organic peroxide such as BPO is used to initiate the reaction, can be used for this polymerization.

[0078] A third aspect of the present invention provides a halogenated grafting agent produced by the manufacturing method described above.

[0079] A fourth aspect of the present invention provides the use of the aforementioned halogenated grafting agent as a grafting agent for producing diene rubber.

[0080] A fifth aspect of the present invention provides a halogenated branched butyl rubber comprising a structural unit E derived from pre-isobutylene, a structural unit F derived from isoprene, and a structural unit G derived from a halogenated grafting agent, wherein the halogenated grafting agent is the aforementioned halogenated grafting agent.

[0081] In some embodiments, the mass ratio of structural unit E, structural unit F, and structural unit G is 100:2 to 6:3 to 8, preferably 100:3 to 5:4 to 7, based on the total weight of the halogenated branched butyl rubber.

[0082] A sixth aspect of the present invention is: The present invention provides a method for producing halogenated branched butyl rubber, comprising the step of cationic polymerization of isobutylene, isoprene, and the aforementioned halogenated grafting agent in the presence of a diluent, an organic solvent, and a co-initiator to obtain the halogenated branched butyl rubber.

[0083] In some embodiments, the mass ratio of isobutylene, isoprene, and the halogenated grafting agent is 100:2 to 6:3 to 8, preferably 100:3 to 5:4 to 7.

[0084] In some embodiments, the diluent is a halogenated alkane, the halogen atom in the halogenated alkane is F, Cl, or Br, and the number of carbon atoms in the halogenated alkane is 1 to 4. Preferably, the diluent is at least one selected from monochloromethane, methylene chloride, carbon tetrachloride, dichloroethane, tetrachloropropane, heptachloropropane, monofluoromethane, difluoromethane, tetrafluoroethane, and carbon tetrafluoride.

[0085] In some embodiments, the solvent is a hydrocarbon solvent, preferably at least one of linear alkanes, aromatic hydrocarbons, and cycloalkanes, and more preferably at least one of pentane, hexane, octane, heptane, cyclohexane, benzene, toluene, xylene, and ethylbenzene.

[0086] In some embodiments, the co-initiator comprises a protonic acid and an alkylaluminum halide, preferably the molar ratio of the protonic acid to the alkylaluminum halide is 1:10 to 100, preferably the protonic acid is at least one selected from HCl, HF, HBr, H2SO4, H2CO3, H3PO4, and HNO3, and the alkylaluminum halide is at least one selected from diethylaluminum monochloride, diisobutylaluminum monochloride, methylaluminum dichloride, ethylaluminum sesquichloride, isobutylaluminum sesquichloride, n-propylaluminum dichloride, isopropylaluminum dichloride, dimethylaluminum chloride, and ethylaluminum chloride.

[0087] In some embodiments, the mass ratio of isobutylene to the co-initiator is 100:0.01 to 0.5.

[0088] In some embodiments, the conditions for cationic polymerization include a polymerization temperature of -100°C to -80°C and a cationic polymerization time of 3 to 4 hours.

[0089] A seventh aspect of the present invention provides halogenated branched butyl rubber obtained by the manufacturing method described above. The halogenated branched butyl rubber of the present invention is preferably brominated branched butyl rubber.

[0090] An eighth aspect of the present invention provides the use of the aforementioned halogenated branched butyl rubber in many fields, such as automobiles and electronic and electrical equipment.

[0091] In preferred embodiments of the present invention, the halogenated grafting agent is a linear block copolymer obtained by polymerizing isoprene, 1,3-butadiene, p-alkylstyrene, and vinyl bromide.

[0092] In a particularly preferred embodiment of the present invention, the method for producing the halogenated grafting agent described above specifically includes the following steps. S1: Based on 100 parts by mass of vinyl bromide, first, an inert gas is introduced into a 15L stainless steel reaction vessel with a jacket and purged 2 to 4 times. Then, 100 to 200 parts of solvent, 100 parts of vinyl bromide, and 0.2 to 0.5 parts of molecular weight adjuster are added sequentially to the reaction vessel, stirred and mixed, and heated. When the temperature of the reaction vessel reaches 50 to 60°C, 0.01 to 0.15 parts of the first initiator are added and the mixture is reacted for 4 to 6 hours. After that, 1 to 4 parts of 1,3-butadiene are added to the polymerization vessel and capping is performed. The mixture is reacted for 20 to 40 minutes until the free monomers are gone. After the reaction is complete, the mixture is washed and baked to obtain a polymer brominater. S2: The total mass of the reaction monomers is made to 100%. First, argon is introduced into a 15L stainless steel reaction vessel with a jacket and substituted 2 to 4 times. 200% to 300% of the solvent, 60% to 80% of p-alkylstyrene, and 0.3% to 0.5% of the structural modifier are added sequentially to the polymerization vessel. After raising the temperature to 60 to 70°C, the second initiator is added and the reaction is carried out for 70 to 90 minutes. Then, 20% to 40% of the polymer brominater and 0.1% to 0.2% of the structural modifier are further added to the polymerization vessel, the temperature is raised to 80 to 90°C, and the reaction is carried out for 80 to 100 minutes. Finally, 3 to 5 parts of isoprene are added to the polymerization vessel and capping is performed. The reaction is carried out for 30 to 40 minutes until the free monomers are gone. The paste is then aggregated by a wet method and baked to obtain the halogenated grafting agent.

[0093] According to a particularly preferred embodiment of the present invention, a method for producing halogenated branched butyl rubber using the above-mentioned halogenated grafting agent specifically includes the following steps:

[0094] First, using isobutylene as the reaction monomer, the mass was reduced to 100%. Nitrogen was introduced into a 4L stainless steel reaction vessel with a jacket and purged 3 to 5 times. Then, 100% to 200% mixed solvent (diluent / solvent V:V ratio of 70 to 30 / 30 to 70) and 4% to 7% of the halogenated grafting agent prepared above were added to the polymerization vessel, and the mixture was stirred for 40 to 60 minutes to dissolve the grafting agent completely. Subsequently, the temperature is lowered to -80 to -70°C, and 100% to 200% of the diluent, 100% of isobutylene, and 3% to 5% of isoprene are added. The mixture is stirred and mixed until the polymerization system temperature drops to -90 to -80°C. Then, 10% to 20% of the diluent and 0.01% to 0.5% of the co-initiator are mixed under conditions of -100 to -90°C and aged for 40 to 50 minutes. After adding this mixture to the polymerization system, the reaction is stirred for 3 to 4 hours. Finally, 4% to 7% of the stopper is added, the material is removed, and it is subjected to aggregation, washing, and drying to obtain a high-attenuation halogenated branched butyl rubber product.

[0095] The present invention will be described in detail below with reference to examples.

[0096] Unless specific conditions are indicated in the following examples and comparative examples, they shall be carried out under normal conditions or conditions suggested by the manufacturer. Unless otherwise specified, the reagents and equipment used are all common commercially available products. The mass ratio relationship between the produced multi-component copolymer product and each structural unit contained in the halogenated branched butyl rubber is determined according to the amount of raw materials used.

[0097] (1) Origin of raw materials: 1,3-Butadiene: Polymerization grade, purchased from China Petroleum Lanzhou Petrochemical Company. Isobutylene, Isoprene: Polymerization grade, purchased from Zhejiang Xinhui New Materials Co., Ltd. p-Methylstyrene: Polymerization grade, purchased from Jiande Bofeng Chemical Co., Ltd. PN-Butylstyrene: Polymerization grade, purchased from Luoyang Boyu Energy Technology Co., Ltd. Vinyl bromide: Polymerized grade, purchased from Wuhan Fuxinyuan Technology Co., Ltd. Benzoyl peroxide (BPO): Purchased from Lanzhou Auxiliary Chemicals Co., Ltd. n-butyllithium: 98% purity, purchased from Nanjing Tonglian Chemical Co., Ltd. Ethyl aluminum sesquichloride: 98% purity, purchased from Bailingwei Technology Co., Ltd. The other reagents are commercially available industrial products.

[0098] (2) Analysis and testing methods Measurement of bromine content: A 10 mg sample is weighed and the sample is thermally decomposed using a Q600 TG / DTG thermogravimetric analyzer under a nitrogen atmosphere at a heating rate of 10°C / min and a flow rate of 50 mL / min. In the first stage of thermal decomposition, bromine units in the sample are debrominated to form HBr, and the bromine content (X) in the sample is estimated using the percentage of the formed HBr, with the calculation formula shown below.

number

[0099] In the examples and comparative examples of the present invention, the mass ratio of monomer input is equal to the mass ratio of the corresponding structural units in the halogenated grafting agent produced. Manufacturing Example 1

[0100] (1) Production of polymer brominated agent: First, argon was introduced into a 15L stainless steel reaction vessel with a jacket and purged twice. 1000g of cyclohexane, 1000g of vinyl bromide, and 2g of tert-dodecyl mercaptan were added to the reaction vessel in order, stirred and mixed, and heated. When the temperature of the reaction vessel reached 50°C, 0.1g of BPO was added and the reaction was carried out for 4 hours. Then, 10g of 1,3-butadiene was added to the polymerization vessel and capping was performed. The reaction was carried out for 20 minutes until the free monomers were gone. After the reaction was complete, the mixture was washed and baked to obtain 1010g of polymer brominated agent containing 10g of structural unit B (1,3-butadiene). (2) Preparation of halogenated grafting agent: First, argon was introduced into a 15L stainless steel reaction vessel with a jacket and purged twice. In the polymerization vessel, 2000g of cyclohexane, 600g of p-methylstyrene, and 3g of THF were added in order, and the temperature was raised to 60°C. N-butyllithium 14.6 mmol was added and the reaction was carried out for 70 minutes. Then, 400g of polymer brominater (containing 4g of structural unit B) and 1g of THF were added to the polymerization vessel, and the temperature was further raised to 80°C and the reaction was carried out for 80 minutes. Finally, 30g of isoprene was added to the polymerization vessel, and a capping reaction was carried out for 30 minutes until the free monomers were gone. The paste was then agglomerated by a wet method and baked. p-methylstyrene , 1,3-butadiene, vinyl bromide A halogenated grafting agent S1 was obtained, having a mass ratio of structural units derived from isoprene of 100:0.67:67:5. The detection results showed that for halogenated grafting agent S1, the Mn content was 30350, the Mw / Mn ratio was 2, the bromine content was 5.97%, and the apparent viscosity at 25°C was 8 mPa·s. As can be seen from Figure 1, wavenumber 3005-3100 cm -1shows an asymmetric stretching vibration doublet absorption peak of the benzene ring, with a wave number of 2950 - 2800 cm -1 shows a stretching vibration absorption peak of methyl (CH3), with a wave number of 1680 - 1500 cm -1 shows a stretching vibration absorption peak of "carbon - carbon double bond", with a wave number of 900 - 850 cm -1 shows a stretching vibration single absorption peak of para - substitution of the benzene ring, with a wave number of 700 - 650 cm -1 shows a stretching vibration single absorption peak of bromine atoms. From this, it is clear that the halogenated grafting agents produced from vinyl bromide, 1,3 - butadiene, p - methylstyrene, and isoprene contain para - methylbenzene structures and bromine - substitution structures. Production Example 2

[0101] (1) Production of polymer brominating agent: First, introduce argon into a 15L stainless steel reaction kettle with a jacket and replace it twice. Then, add 1200 g of cyclohexane, 1000 g of vinyl bromide, and 2.5 g of tert - dodecyl mercaptan to the reaction kettle in sequence, stir and mix, heat, and when the temperature of the reaction kettle reaches 52 °C, add 0.4 g of BPO and react for 4.5 h. Then, add 15 g of 1,3 - butadiene to the polymerization kettle for capping and react for 26 min until there is no free monomer left. After the reaction is completed, wash and bake to obtain 1015 g of polymer brominating agent. (2) Production of halogenated grafting agent: First, introduce argon into a 15L stainless steel reaction kettle with a jacket and replace it twice. Then, add 2100 g of cyclohexane, 650 g of p - methylstyrene, and 3.5 g of THF to the polymerization kettle in sequence, heat up to 62 °C, add 14.9 mmol of n - butyl lithium and react for 74 min. Then, add 350 g of polymer brominating agent and 1.2 g of THF to the polymerization kettle, further heat up to 82 °C, and react for 85 min. Finally, add 35 g of isoprene to the polymerization kettle and perform a capping reaction for 32 min until there is no free monomer left. Coagulate the paste solution by the wet method and bake, p-methylstyrene , 1,3 - butadiene, vinyl bromideA halogenated grafting agent S2 was obtained, having a mass ratio of structural units derived from isoprene of 100:0.77:54:5.4. The detection results showed that for halogenated grafting agent S2, the Mn content was 31500, the Mw / Mn ratio was 2.3, the bromine content was 5.63%, and the apparent viscosity at 25°C was 12 mPa·s. Manufacturing Example 3

[0102] (1) Production of polymer brominated agent: First, argon was introduced into a 15L stainless steel reaction vessel with a jacket and purged three times. 1500g of cyclohexane, 1000g of vinyl bromide, and 3g of tert-dodecyl mercaptan were added to the reaction vessel in order, stirred and mixed, and heated. When the temperature of the reaction vessel reached 54°C, 0.7g of BPO was added and the reaction was carried out for 5 hours. Then, 20g of 1,3-butadiene was added to the polymerization vessel and capping was performed. The reaction was carried out for 30 minutes until the free monomers were gone. After the reaction was complete, the mixture was washed and baked to obtain 1020g of polymer brominated agent. (2) Preparation of halogenated grafting agent: First, argon was introduced into a 15L stainless steel reaction vessel with a jacket and purged three times. In the polymerization vessel, 2300g of cyclohexane, 700g of p-methylstyrene, and 4g of THF were added in order, and the temperature was raised to 64°C. 15.5 mmol of n-butyllithium was added and the reaction was carried out for 78 minutes. Then, 300g of polymer brominated agent and 1.4g of THF were added to the polymerization vessel, and the temperature was further raised to 85°C and the reaction was carried out for 90 minutes. Finally, 40g of isoprene was added to the polymerization vessel, and a capping reaction was carried out for 34 minutes until the free monomers were gone. The paste was then agglomerated by a wet method and baked. p-methylstyrene , 1,3-butadiene, vinyl bromide A halogenated grafting agent S3 was obtained, in which the mass ratio of structural units derived from isoprene was 100:0.86:43:5.7. The detection results showed that for halogenated grafting agent S3, the Mn content was 33600, the Mw / Mn ratio was 2.7, the bromine content was 5.03%, and the apparent viscosity at 25°C was 17 mPa·s. Manufacturing Example 4

[0103] (1) Production of polymer brominated agent: First, argon was introduced into a 15L stainless steel reaction vessel with a jacket and purged three times. 1700g of cyclohexane, 1000g of vinyl bromide, and 4g of tert-dodecyl mercaptan were added to the reaction vessel in order, stirred and mixed, and heated. When the temperature of the reaction vessel reached 56°C, 0.9g of BPO was added and the reaction was carried out for 5.3 hours. Then, 30g of 1,3-butadiene was added to the polymerization vessel and capping was performed. The reaction was carried out for 30 minutes until the free monomers were gone. After the reaction was complete, the mixture was washed and baked to obtain 1030g of polymer brominated agent. (2) Preparation of halogenated grafting agent: First, argon was introduced into a 15L stainless steel reaction vessel with a jacket and purged three times. Then, 2500g of cyclohexane, 730g of p-methylstyrene, and 4.4g of THF were added in sequence to the polymerization vessel, and the temperature was raised to 66°C. 16.1m of n-butyllithium was added and the reaction was carried out for 80 minutes. Subsequently, 270g of polymer brominated agent and 1.7g of THF were added to the polymerization vessel, and the temperature was further raised to 87°C and the reaction was carried out for 93 minutes. Finally, 43g of isoprene was added to the polymerization vessel, and a capping reaction was carried out for 36 minutes until the free monomers were gone. The paste was then agglomerated by a wet method and baked. p-methylstyrene , 1,3-butadiene, vinyl bromide A halogenated grafting agent S4 was obtained, having a mass ratio of structural units derived from isoprene of 100:1.1:38:5.9. The detection results showed that for halogenated grafting agent S4, the Mn content was 36100, the Mw / Mn ratio was 3, the bromine content was 4.68%, and the apparent viscosity at 25°C was 23 mPa·s. Manufacturing Example 5

[0104] (1) Production of polymer brominated agent: First, argon was introduced into a 15L stainless steel reaction vessel with a jacket and purged four times. 1800g of cyclohexane, 1000g of 2-bromo-1-propene, and 4.5g of tert-dodecyl mercaptan were added to the reaction vessel in order, stirred and mixed, and heated. When the temperature of the reaction vessel reached 58°C, 1.2g of BPO was added and the reaction was carried out for 5.6 hours. Then, 35g of 1,3-butadiene was added to the polymerization vessel and capping was performed. The reaction was carried out for 35 minutes until the free monomers were gone. After the reaction was complete, the mixture was washed and baked to obtain 1035g of polymer brominated agent. (2) Preparation of halogenated grafting agent: First, argon was introduced into a 15L stainless steel reaction vessel with a jacket and purged four times. In the polymerization vessel, 2700g of cyclohexane, 760g of p-ethylstyrene, and 4.8g of THF were added in order, and the temperature was raised to 68°C. 16.8mmo1 of n-butyllithium was added and the reaction was carried out for 85 minutes. Then, 240g of polymer brominated agent and 1.9g of THF were added to the polymerization vessel, and the temperature was further raised to 88°C and the reaction was carried out for 96 minutes. Finally, 45g of isoprene was added to the polymerization vessel, and a capping reaction was carried out for 38 minutes until the free monomers were gone. The paste was then agglomerated by a wet method and baked. p-ethylstyrene , 1,3-butadiene, 2-Bromo-1-Propene A halogenated grafting agent S5 was obtained, having a mass ratio of structural units derived from isoprene of 100:1.1:38:5.9. The detection results showed that for halogenated grafting agent S5, the Mn content was 38200, the Mw / Mn ratio was 3.3, the bromine content was 4.45%, and the apparent viscosity at 25°C was 26 mPa·s. Manufacturing Example 6

[0105] (1) Production of polymer brominater: First, argon was introduced into a 15L stainless steel reaction vessel with a jacket and purged four times. 2000g of cyclohexane, 1000g of 2-bromo-1-butene, and 5g of tert-dodecyl mercaptan were added to the reaction vessel in order, stirred and mixed, and heated. When the temperature of the reaction vessel reached 60°C, 1.5g of DCP was added and the reaction was carried out for 6 hours. Then, 40g of 1,3-butadiene was added to the polymerization vessel and capping was performed. The reaction was carried out for 40 minutes until the free monomers were gone. After the reaction was complete, the mixture was washed and baked to obtain 1040g of polymer brominater. (2) Preparation of halogenated grafting agent: First, argon was introduced into a 15L stainless steel reaction vessel with a jacket and purged four times. 3000g of cyclohexane, 800g of pn-butylstyrene, and 5g of THF were added sequentially to the polymerization vessel, and the temperature was raised to 70°C. 17.3mO1 of n-butyllithium was added and the reaction was carried out for 90 minutes. Then, 200g of polymer brominated agent and 2g of THF were added to the polymerization vessel, and the temperature was raised again to 90°C and the reaction was carried out for 100 minutes. Finally, 50g of isoprene was added to the polymerization vessel, and a capping reaction was carried out for 40 minutes until the free monomers were gone. The paste was then agglomerated and baked using a wet method. pn-butylstyrene , 1,3-butadiene, 2-Bromo-1-Butene A halogenated grafting agent S6 was obtained, having a mass ratio of structural units derived from isoprene of 100:1:25:6.25. The detection results showed that for halogenated grafting agent S6, the Mn content was 39600, the Mw / Mn ratio was 3.5, the bromine content was 4.12%, and the apparent viscosity at 25°C was 30 mPa·s. Manufacturing example 7

[0106] The halogenated grafting agent was prepared in the same manner as in Production Example 1, except that the amount of 1,3-butadiene added during the manufacturing process was 20 g. p-methylstyrene , 1,3-butadiene, vinyl bromide A halogenated grafting agent S7 was obtained, having a mass ratio of structural units derived from isoprene of 100:1.34:67:5. The detection results showed that for halogenated grafting agent S7, the Mn content was 30600, the Mw / Mn ratio was 2.1, the bromine content was 5.92%, and the apparent viscosity at 25°C was 9.2 mPa·s. Manufacturing Example 8

[0107] The halogenated grafting agent was prepared according to the method of Production Example 1, except that 30 g of 1,3-butadiene was added during the manufacturing process. p-methylstyrene , 1,3-butadiene, vinyl bromide A halogenated grafting agent S8 was obtained, having a mass ratio of structural units derived from isoprene of 100:1.94:67:5. The detection results showed that for halogenated grafting agent S8, the Mn content was 31,000, the Mw / Mn ratio was 2.2, the bromine content was 5.91%, and the apparent viscosity at 25°C was 11.2 mPa·s. Manufacturing Example 9

[0108] The halogenated grafting agent was produced in the same manner as in Production Example 1, except that the amount of p-methylstyrene added during the manufacturing process was 700 g. p-methylstyrene , 1,3-butadiene, vinyl bromide A halogenated grafting agent S9 was obtained, having a mass ratio of structural units derived from isoprene of 100:0.57:57:4. The detection results showed that for halogenated grafting agent S9, the Mn content was 33000, the Mw / Mn ratio was 2.5, the bromine content was 5.23%, and the apparent viscosity at 25°C was 16 mPa·s. Manufacturing Example 10

[0109] The halogenated grafting agent was produced in the same manner as in Production Example 1, except that the amount of p-methylstyrene added during the manufacturing process was 800 g. p-methylstyrene , 1,3-butadiene, vinyl bromide A halogenated grafting agent S10 was obtained, having a mass ratio of structural units derived from isoprene of 100:0.49:50:4. The detection results showed that for halogenated grafting agent S10, the Mn content was 35,000, the Mw / Mn ratio was 2.9, the bromine content was 4.76%, and the apparent viscosity at 25°C was 26 mPa·s. Manufacturing Example 11

[0110] The halogenated grafting agent was produced in the same manner as in Production Example 1, except that vinyl bromide was replaced with vinyl chloride during the manufacturing process, and the remaining conditions were the same as in Production Example 1. p-methylstyrene , 1,3-butadiene, polyvinyl chloride A halogenated grafting agent S11 was obtained, having a mass ratio of structural units derived from isoprene of 100:0.67:67:5. The detection results showed that for halogenated grafting agent S11, the Mn content was 30100, the Mw / Mn ratio was 2.1, the chlorine content was 5.72%, and the apparent viscosity at 25°C was 5.7 mPa·s. Manufacturing Example 12

[0111] Argon was introduced into a 15L stainless steel reaction vessel with a jacket and purged twice. 1000g of cyclohexane, 1000g of vinyl bromide, 600g of p-methylstyrene, and 2g of tert-dodecyl mercaptan were added to the reaction vessel in order, stirred and mixed, and heated. When the temperature of the reaction vessel reached 50°C, 0.1g of BPO was added and the reaction was carried out for 4 hours. Finally, 30g of isoprene was added to the polymerization vessel and the capping reaction was carried out for 30 minutes until the free monomers were gone. The paste was agglomerated and baked by a wet method to obtain halogenated grafting agent S12, in which the mass ratio of structural units derived from vinyl bromide, p-methylstyrene, and isoprene was 100:17:5. The detection results showed that for halogenated grafting agent S12, the Mn content was 50,000, the Mw / Mn ratio was 4, the bromine content was 12.1%, and the apparent viscosity at 25°C was 35 mPa·s. Manufacturing Example 13

[0112] In the halogenated grafting agent manufacturing process of step (2), the halogenated grafting agent is manufactured under the same conditions as in Manufacturing Example 1, except that the amount of polymer brominated agent added is 200 g. p-methylstyrene, 1,3-butadiene, vinyl bromide A halogenated grafting agent S13 was obtained, having a mass ratio of structural units derived from isoprene of 100:0.34:33:5. The detection results showed that for halogenated grafting agent S13, the Mn content was 25,000, the Mw / Mn ratio was 1.5, the bromine content was 4.91%, and the apparent viscosity at 25°C was 5 mPa·s. Manufacturing Example 14

[0113] In the halogenated grafting agent manufacturing process of step (2), the halogenated grafting agent is manufactured under the same conditions as in manufacturing example 1, except that the amount of polymer brominated agent added is 300 g. p-methylstyrene , 1,3-butadiene, vinyl bromide A halogenated grafting agent S14 was obtained, having a mass ratio of structural units derived from isoprene of 100:0.5:50:5. The detection results showed that for halogenated grafting agent S14, the Mn content was 28,000, the Mw / Mn ratio was 1.7, the bromine content was 5.38%, and the apparent viscosity at 25°C was 7 mPa·s. Manufacturing Comparison Example 1

[0114] During the halogenated grafting agent manufacturing process in step (2), the halogenated grafting agent was manufactured under the same conditions as in Manufacturing Example 1, except that p-methylstyrene was replaced with styrene. styrene , 1,3-butadiene, vinyl bromide And, a halogenated grafting agent D1 was obtained in which the mass ratio of structural units derived from isoprene was 100:0.67:67:5. The detection results showed that for halogenated grafting agent D1, the Mn content was 23,000, the Mw / Mn ratio was 1.9, the bromine content was 5.98%, and the apparent viscosity at 25°C was 3.8 mPa·s. Manufacturing Comparison Example 2

[0115] Step (1) During the manufacturing process of the polymer brominater, the halogenated grafting agent is manufactured under the same conditions as in Manufacturing Example 1, except that vinyl bromide is replaced with ethylene. p-methylstyrene , 1,3-butadiene, ethylene A halogenated grafting agent D2 was obtained, having a mass ratio of structural units derived from isoprene of 100:0.67:67:5. The detection results showed that for halogenated grafting agent D2, Mn was 21000, Mw / Mn was 2.4, bromine content was 0%, and apparent viscosity at 25°C was 3.1 mPa·s. Example 1

[0116] First, nitrogen was introduced into a 4L stainless steel reaction vessel with a jacket and purged three times. 700g of monochloromethane and 300g of cyclohexane were added to the polymerization vessel, and 20g of halogenated grafting agent S1 obtained in Production Example 1 was added. The mixture was stirred for 40 minutes to dissolve completely. Subsequently, after cooling to -70°C, 500g of monochloromethane, 500g of isobutylene, and 15g of isoprene were added in sequence, and the mixture was stirred until the polymerization system temperature dropped to -80°C. Then, 50g of monochloromethane, 1.05g of ethylaluminum sesquichloride, and 0.011g of HCl were mixed and aged at -90°C for 40 minutes, and then added all at once to the polymerization system and stirred for 3 hours to react. Finally, 20g of methanol was added, and the material was removed, flocculated, washed, and dried to obtain a brominated branched butyl rubber product in which the mass ratio of structural units derived from isobutylene, isoprene, and halogenated grafting agent S1 was 100:3:4. Sample collection and analysis: Standard samples were prepared, and the test characteristics are shown in Table 1. Examples 2-14

[0117] Brominated branched butyl rubber products were manufactured in the same manner as in Example 1, except that halogenated grafting agent S1 was replaced with any one of halogenated grafting agents S2 to S14, and halogenated branched butyl rubber products were obtained. Sample collection and analysis: Standard samples were prepared, and the test characteristics are shown in Table 1. Example 15

[0118] Brominated branched butyl rubber product was manufactured under the same conditions as in Example 1, except that 25 g of halogenated grafting agent S1 was added during the manufacturing process, to obtain a brominated branched butyl rubber product in which the mass ratio of structural units derived from isobutylene, isoprene, and halogenated grafting agent S1 was 100:3:5. Sample collection and analysis: Standard samples were prepared, and the test characteristics are shown in Table 1. Example 16

[0119] Brominated branched butyl rubber product was manufactured under the same conditions as in Example 1, except that 30 g of halogenated grafting agent S1 was added during the manufacturing process, to obtain a brominated branched butyl rubber product in which the mass ratio of structural units derived from isobutylene, isoprene, and halogenated grafting agent S1 was 100:3:6. Sample collection and analysis: Standard samples were prepared, and the test characteristics are shown in Table 1. Example 17

[0120] Brominated branched butyl rubber product was manufactured under the same conditions as in Example 1, except that 35 g of halogenated grafting agent S1 was added during the manufacturing process, to obtain a brominated branched butyl rubber product in which the mass ratio of structural units derived from isobutylene, isoprene, and halogenated grafting agent S1 was 100:3:7. Sample collection and analysis: Standard samples were prepared, and the test characteristics are shown in Table 1. Example 18

[0121] A brominated branched butyl rubber product was manufactured under the same conditions as in Example 1, except that 20 g of isoprene was added during the manufacturing process, to obtain a brominated branched butyl rubber product in which the mass ratio of structural units derived from isobutylene, isoprene, and halogenated grafting agent S1 was 100:4:4. Sample collection and analysis: Standard samples were prepared, and the test characteristics are shown in Table 1. Example 19

[0122] A brominated branched butyl rubber product was manufactured under the same conditions as in Example 1, except that 25 g of isoprene was added during the manufacturing process, to obtain a brominated branched butyl rubber product in which the mass ratio of structural units derived from isobutylene, isoprene, and halogenated grafting agent S1 was 100:5:4. Sample collection and analysis: Standard samples were prepared, and the test characteristics are shown in Table 1. Example 20

[0123] Brominated branched butyl rubber product was produced using the same method as in Example 1, except that 1.05 g of ethylaluminum sesquichloride and 0.011 g of HCl were replaced with 1.05 g of aluminum trichloride. Sample collection and analysis: Standard samples were prepared, and their test characteristics are shown in Table 1. Comparative Example 1

[0124] Brominated branched butyl rubber product was manufactured using the same method as in Example 1, except that halogenated grafting agent S1 was replaced with halogenated grafting agent D1. Sample collection and analysis: Standard samples were prepared, and their test characteristics are shown in Table 1. Comparative Example 2

[0125] Brominated branched butyl rubber product was manufactured using the same method as in Example 1, except that halogenated grafting agent S1 was replaced with halogenated grafting agent D2. Sample collection and analysis: Standard samples were prepared, and their test characteristics are shown in Table 1.

[0126] [Table 1]

[0127] The results in Table 1 show that, compared to the comparative examples, the halogenated branched butyl rubber products manufactured in the examples of the present invention have superior damping performance, superior airtightness, and superior mechanical properties.

[0128] Although preferred embodiments of the present invention have been described in detail above, the present invention is not limited thereto. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical proposal of the present invention, and these simple modifications and combinations, including combining each technical feature in other appropriate ways, should also be considered as part of the disclosures of the present invention and all fall within the scope of protection of the present invention.

Claims

1. A halogenated grafting agent characterized by containing structural unit A, structural unit B, structural unit C, and structural unit D, wherein structural unit A has the structure shown in formula (1), structural unit C has the structure shown in formula (2), structural unit B is connected to structural unit A and structural unit C respectively, structural unit D is a terminal capping structural unit, structural unit B and structural unit D are each independently derived from a conjugated diene, the conjugated diene is butadiene and / or isoprene, and the mass ratio of structural unit A, structural unit B, structural unit C, and structural unit D is 100:0.34 to 1.94:25 to 67:4 to 6.

25. 【Chemistry 1】 (Here, R 1 and R 2 are each independently hydrogen or a linear or branched alkyl of C 1 to C 5 , R 3 is a linear or branched alkyl of C 1 to C 8 , R 4 and R 5 are each independently hydrogen or a linear or branched alkyl of C 1 to C 4 , and X is Cl or Br.)

2. R 1 and R 2 Each of them independently consists of hydrogen or C 1 ~C 3 It is a linear or branched alkyl group, R 3 C 1 ~C 5 It is a linear or branched alkyl group, R 4 and R 5 Each of them independently consists of hydrogen or C 1 ~C 2 The halogenated grafting agent according to claim 1, wherein the alkyl group is...

3. The halogenated grafting agent according to claim 1, wherein the structural unit B is derived from butadiene and the structural unit D is derived from isoprene.

4. The halogen content in the halogenated grafting agent is 3 wt% to 7 wt% by mass percentage. and / or, the number average molecular weight of the halogenated grafting agent is 25,000 to 50,000 g / mol, and / or, the molecular weight distribution index of the halogenated grafting agent is 1.5 to 4. and / or, the halogenated grafting agent is a block copolymer or a random copolymer. The halogenated grafting agent according to claim 1, wherein the apparent viscosity of the halogenated grafting agent at 25°C is 5 to 35 mPa·s.

5. Under polymerization reaction conditions, in the presence of an initiator, the monomer represented by formula (I) and the monomer represented by formula (II) are polymerized to obtain a polymerization product. Alternatively, (1) in the presence of a molecular weight modifier, a first solvent, and a first initiator, the first polymerization reaction of the monomer represented by formula (I) is carried out, the second conjugated diene is added to carry out the first capping reaction to obtain the first product, (2) Step S1, in the presence of a structural modifier, a second solvent, and a second initiator, a second polymerization reaction of the monomer represented by formula (II) is carried out to obtain a second product, and then the first product is added thereto to carry out a third polymerization reaction to obtain a third product. Step S2 involves carrying out a second capping reaction between the polymerization product obtained in step S1 or the third product obtained in step (2) and the first conjugated diene to obtain a halogenated grafting agent. A method for producing a halogenated grafting agent, characterized in that the first conjugated diene and the second conjugated diene are each independently butadiene and / or isoprene, and the mass ratio of the monomer represented by formula (I), the second conjugated diene, the monomer represented by formula (II), and the first conjugated diene is 100:0.34 to 1.94:25 to 67:4 to 6.

25. 【Chemistry 2】 (Here, R 1 and R 2 Each of them independently consists of hydrogen or C 1 ~C 5 It is a linear or branched alkyl group, R 3 C 1 ~C 8 It is a linear or branched alkyl group, R 4 and R 5 Each of them independently consists of hydrogen or C 1 ~C 4 It is a linear or branched alkyl group, where X is Cl or Br.

6. The monomer represented by formula (II) is a halogenated olefin. and / or, the monomer represented by formula (I) is p-alkylstyrene, and / or, the first initiator is an organic peroxide, and / or the second initiator is a hydrocarbyl monolithium compound R-Li, where R is C 1 ~C 20 Saturated aliphatic hydrocarbon group, C 3 ~C 20 Alicyclic hydrocarbon group, C 6 ~C 20 The aromatic hydrocarbon group, or a composite group of the above groups, and / or, the molecular weight adjusting agent is at least one selected from tert-decyl mercaptan, tert-dodecyl mercaptan, tert-tetradecyl mercaptan, and tert-hexadecyl mercaptan. and / or, the structural modifier is a polar organic compound, The manufacturing method according to claim 5, wherein the first solvent and the second solvent are each independently a hydrocarbon solvent.

7. The monomer represented by formula (II) is at least one selected from vinyl bromide, vinyl chloride, 1-bromo-1-propene, 2-bromo-1-propene, 1-bromo-1-butene, and 2-bromo-1-butene. and / or the monomer represented by formula (I) is at least one selected from p-methylstyrene, p-ethylstyrene, p-propylstyrene, p-n-butylstyrene, p-isobutylstyrene, and p-isopentylstyrene. and / or, the first initiator is at least one selected from dicumyl peroxide, cumene hydroperoxide, and benzoyl peroxide. and / or, the second initiator is at least one selected from n-butyllithium, sec-butyllithium, methylbutyllithium, phenylbutyllithium, naphthyllithium, cyclohexyllithium, and dodecyllithium. and / or, the structural modifier is at least one selected from diethylene glycol dimethyl ether, tetrahydrofuran, ethyl ether, ethyl methyl ether, anisole, diphenyl ether, glycol dimethyl ether, and triethylamine. The manufacturing method according to claim 6, and / or, the first solvent and the second solvent are each independently at least one selected from pentane, hexane, octane, heptane, cyclohexane, benzene, toluene, xylene, and ethylbenzene.

8. The conditions for the first polymerization reaction include a reaction temperature of 50-60°C and a reaction time of 4-6 hours. and / or the conditions for the first capping reaction include a reaction temperature of 50 to 60°C and a reaction time of 20 to 40 min. and / or the conditions for the second polymerization reaction include a reaction temperature of 60 to 70°C and a reaction time of 70 to 90 min. and / or the conditions for the third polymerization reaction include a reaction temperature of 80 to 90°C and a reaction time of 80 to 100 min. The manufacturing method according to claim 5, and / or the conditions for the second capping reaction include a reaction temperature of 80 to 90°C and a reaction time of 30 to 40 min.

9. Use of the halogenated grafting agent according to any one of claims 1 to 4 as a grafting agent for manufacturing diene rubber.

10. The use according to claim 9, wherein the diene rubber is butyl rubber.

11. A halogenated branched butyl rubber comprising structural unit E derived from isobutylene, structural unit F derived from isoprene, and structural unit G derived from a halogenated grafting agent, wherein the halogenated grafting agent is the halogenated grafting agent described in any one of claims 1 to 4.

12. The halogenated branched butyl rubber according to claim 11, wherein the mass ratio of structural unit E, structural unit F, and structural unit G is 100:2 to 6:3 to 8 based on the total weight of the halogenated branched butyl rubber.

13. A method for producing halogenated branched butyl rubber, comprising the step of cationic polymerization of isobutylene, isoprene, and a halogenated grafting agent according to any one of claims 1 to 4 in the presence of a diluent, an organic solvent, and a co-initiator to obtain halogenated branched butyl rubber.

14. The mass ratio of isobutylene, isoprene, and the halogenated grafting agent is 100:2 to 6:3 to 8. and / or, the diluent is a halogenated alkane, the halogen atom in the halogenated alkane is Cl or Br, and the number of carbon atoms in the halogenated alkane is 1 to 4. and / or, the co-initiator comprises a protonic acid and an alkylaluminum halide, wherein the molar ratio of the protonic acid to the alkylaluminum halide is 1:10 to 100. and / or the mass ratio of isobutylene to the co-initiator is 100:0.01 to 0.5, The manufacturing method according to claim 13, and / or the conditions for cationic polymerization comprising a polymerization temperature of -100°C to -80°C and a cationic polymerization time of 3 to 4 hours.

15. The aforementioned protonates are HCl, HF, HBr, H 2 SO 4 , H 2 CO 3 , H 3 PO 4 , and HNO 3 At least one selected from, The method for producing aluminum chloride according to claim 14, wherein the alkylaluminum halide is at least one selected from diethylaluminum monochloride, diisobutylaluminum monochloride, methylaluminum dichloride, ethylaluminum sesquichloride, isobutylaluminum sesquichloride, n-propylaluminum dichloride, isopropylaluminum dichloride, dimethylaluminum chloride, and ethylaluminum chloride.

16. Use of halogenated branched butyl rubber according to claim 11 in automobiles and electronic and electrical devices.

17. Use of halogenated branched butyl rubber according to claim 12 in automobiles and electronic and electrical devices.

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